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Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by
same

Abstract
CN102423642B
The invention relates to a permanent hydrophilic modification method for the surface of a porous
China
membrane. The method comprises the following steps of: soaking a porous membrane with a
polymer containing the solution of a vinyl alcohol chain segment, a first solvent and deionized water;
evaporating to remove the solvent so that the hydrophilic polymer is adsorbed on the surface of the Download PDF Find Prior Art Similar
porous membrane and the surface of the membrane pores; and performing a cross-linking reaction
with a cross-linking agent and the hydrophilic macromolecules adsorbed on the membrane surface Other languages: Chinese
to form a mesh-like hydrophilic polymer thin layer on the outer side of the porous membrane.
Inventor: 陈亦力, 林勇, 吴强, 芮玉青
Through the method provided by the invention, the flux reduction caused by pore blocking can be
completely avoided, the generated hydrophilic coating is firmer, and the hydrophilic treatment effect Current Assignee : Beijing Originwater Technology Co Ltd
is good.

Worldwide applications

2011 CN

Application CN2011104150451A events

2011-12-13 Application filed by Beijing Originwater


Technology Co Ltd

2011-12-13 Priority to CN2011104150451A

2012-04-25 Publication of CN102423642A

2013-12-11 Application granted

2013-12-11 Publication of CN102423642B

Status Active

2031-12-13 Anticipated expiration

Info: Patent citations (8), Cited by (20), Legal events, Similar


documents, Priority and Related Applications

External links: Espacenet, Global Dossier, Discuss

Claims (9) Hide Dependent


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8/13/23, 1:58 PM CN102423642B - Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same - Google Patents
( )

1. a porous film surface permanent hydrophilic method of modifying is characterized in that the step of the method is as follows:

A, 100 parts of gross weights of preparation containing vinyl alcohol segmented polymer solution: will be dissolved in the mixed solvent is comprised of the first solvent and
deionized water containing the vinyl alcohol segmented polymer, what obtain containing by the 0.2-20 weight portion that vinyl alcohol segmented polymer, 60-94.8 weight
portion the first solvent and 5-30 parts by weight of deionized water form contains vinyl alcohol segmented polymer solution;

Described perforated membrane is polyolefin, polyamide, fluorinated polymer, polyether sulfone, cellulose, PEI, polyacrylonitrile, polyvinyl chloride or ceramic porous membrane;

Described containing the vinyl alcohol segmented polymer be one or more be selected from polyvinyl alcohol, ethylene-vinyl alcohol copolymer, AA-E alcohol copolymer, vinyl
alcohol-vinyl acetate co-polymer, polyvinyl formal, polyvinyl acetal, polyvinyl formal acetal, polyvinyl butyral resin containing the vinyl alcohol segmented polymer;

Described the first solvent is selected from one or more in methyl alcohol, ethanol, isopropyl alcohol or normal propyl alcohol;

B, described perforated membrane is immersed in to prepared by steps A containing in vinyl alcohol segmented polymer solution, soak 10-18h under temperature 25-40 ℃,
generate one deck containing vinyl alcohol segmented polymer layer on described perforated membrane, then separate the perforated membrane containing vinyl alcohol
segmented polymer layer;

C, the perforated membrane that step B is obtained dry naturally, allow the solvent of perforated membrane absorption evaporate, and make to contain the Polymer adsorption
of vinyl alcohol segment on porous film surface and inner hole wall;

D, the perforated membrane dried that step C is obtained are immersed in the aqueous solution that contains 0.1-10% crosslinking agent by weight, allow and carry out cross-
linking reaction 0.5-5h containing vinyl alcohol segmented polymer and described crosslinking agent under temperature 15-60 ℃, form the perforated membrane with network-
like hydrophilic polymer thin layer;

Described crosslinking agent is selected from one or more in borax, formaldehyde, glyoxal or glutaraldehyde;

E, the perforated membrane that step D is obtained separate with the solution that contains crosslinking agent, then put into deionized water and carry out rinsing, remove
unreacted crosslinking agent, obtain a kind of perforated membrane with hydrophilic coating.

2. method according to claim 1, is characterized in that described perforated membrane is hollow fiber porous film or plate porous membrane.

3. method according to claim 1, is characterized in that in steps A, contains the vinyl alcohol segmented polymer 50~80 ℃ of temperature and keep the condition of
constant temperature to be dissolved.

4. method according to claim 1, is characterized in that in steps A, and the described vinyl alcohol segmented polymer solution that contains is comprised of containing
vinyl alcohol segmented polymer, 70-85 weight portion the first solvent and 10-20 parts by weight of deionized water the 2-16 weight portion.

5. method according to claim 1, is characterized in that in step C, and described perforated membrane dries under temperature 15-25 ℃ in the air of natural flow.

6. method according to claim 1, is characterized in that in step D, and the perforated membrane dried is immersed in the aqueous solution that contains 2-8% crosslinking
agent by weight.

7. method according to claim 1, is characterized in that in step D, containing vinyl alcohol segmented polymer and described crosslinking agent, under temperature 20-40
℃, carries out cross-linking reaction 1.5-3.0h.

8. method according to claim 1, is characterized in that in step e, rinsing in deionized water 3-5 time for the perforated membrane obtained at step D, and the amount of
deionized water of use is 5-10 with the ratio of its perforated membrane amount by weight.

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9. according to the perforated membrane with surperficial permanent hydrophilic that in claim 1-8, the described method of any one claim obtains, the pure water flux
that it is characterized in that it is 1300-1900L/m 2h0.1MPa, contact angle is 50-55 °.

Description

A kind of permanent hydrophilic method of modifying of porous film surface and the perforated membrane that adopts described method to obtain

[technical field]

The present invention relates to belong to the porous membrane field.More specifically, the present invention relates to a kind of permanent hydrophilic method of
modifying of porous film surface, also relate to the perforated membrane with surperficial permanent hydrophilic that adopts described method to obtain.

[background technology]

As a kind of new separation technology of green high-efficient, perforated membrane has bright prospects at separation field.At present, the film pollution is still the
bottleneck of restriction diffusion barrier application efficiency.Common porous film material mostly is hydrophobic polymer, thereby filtration resistance is large, easy
absorption lyophobic dust and polluting in filter process.It is to solve film to pollute that perforated membrane is carried out to hydrophilic modifying, reduces the
effective way of operating pressure.The hydrophilic modifying of perforated membrane mainly contains three kinds of approach: develop hydrophily material of preparing
preferably 1.; 2. by masking after hydrophilic macromolecule and existing material of preparing blend; 3. existing material of preparing carries out hydrophilic modifying
to perforated membrane after making perforated membrane by existing technique.The 1st kind of method relates to the exploitation of novel material of preparing, the
ability that film manufacturer does not possess the material of preparing exploitation and produces usually, and therefore this method of modifying difficulty is larger.The
2nd kind of method is the method for modifying of commonly using the most, but during hydrophilic modifying agent the most commonly used only has after perforated
membrane generates such as polyvinylpyrrolidone, polyvinyl alcohol etc. and remains in film on a small quantity, and this part residual hydrophilic macromolecule can run
off gradually in the use procedure of film, makes film recover its hydrophobic property.The 3rd kind of method of modifying just carries out after perforated membrane
forms, and do not change film-forming process, thereby can when keeping the perforated membrane good characteristic, improve to a certain extent its hydrophily,
thereby improves the antifouling property of perforated membrane.The method of surface modification mainly is divided into chemical surface treatment, chemical graft,
surface coating etc.Chemical surface treatment is mainly to introduce active group by methods such as plasmas on the film surface, but adopts the active group of the
introducing of this method can be embedded in gradually in the macromolecule body with high molecular chain rotation, thereby hydrophily is lost gradually; The method
of chemical graft can be brought on the film surface comparatively lasting hydrophily, but the process control more complicated, the chain length of chemical graft is
wayward, and the grafting process easily causes Pore Blocking.The method that surface applies is the method that corresponding use is wider, and its process is simple,
and hydrophilic treatment is effective.The method that is used in conjunction with some chemical crosslinkings in the process that surface applies makes to be coated in
that the material on film surface is crosslinked can access permanent hydrophilic modifying product.Patent WO 2004/022201 A1 has introduced a kind of hydrophilic
monomer of ultraviolet light cross-linking that adopts perforated membrane has been processed, and then uses the polymerization of ultraviolet light trigger monomer,
thereby has generated crosslinked hydrophilic coating.But this method is processed and is only limited to process a small amount of film silk, and is difficult to initiated
polymerization on the fenestra inwall, there is no the heavy industrialization application prospect.Patent CN 101485960A adopts polyvinylidene fluoride porous film to be
soaked in the aqueous solution of polyvinyl alcohol based polymer and aldehyde compound, and then film being soaked in to the aminated compounds aqueous solution
of phosphoric acid, vinyl alcohol compound and aldehyde compound will carry out crosslinked under the catalysis of phosphoric acid.In this patent because the vinyl
alcohol compound of selecting is dissolved in water, that is to say that selected vinyl alcohol compound and water have better compatibility, therefore be difficult to be
adsorbed on hydrophobic polyvinylidene fluoride film surface, vinyl alcohol compound and aldehyde compound will preferentially occur crosslinked in fenestra, form
cross-linking products, thereby cause Pore Blocking.Propose in Chinese patent CN 1792419A to filter aldehydes solution with Polyolefin Hollow Fiber, then use this
doughnut membrane filtration and vinyl alcohol and polyethylene glycol or polyvinylpyrrolidone or its mixture, carry out again crosslinked after having filtered under 15~
65 ℃.Due to the macromolecular materials such as the aldehyde compound of selecting and polyvinyl alcohol be all fully water miscible, crosslinked probability occurs
and is greater than and is adsorbed on the crosslinked probability of generation on membranous wall in hydrophilic macromolecule in fenestra, the flux that therefore is
difficult to avoid plug-hole to cause descends.

In the present invention, the proposition of our initiative adopts a class to be dissolved in double solvents, the hydrophilic macromolecule that can not be dissolved in
separately water is processed film, and the hydrophilic macromolecule of this class, containing a certain proportion of hydrophobic segment, has guaranteed that
macromolecule can be adsorbed on hydrophobic polymeric membrane surface smoothly.Polymeric membrane is dissolved with in immersion after the solution of

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hydrophilic high mol to take out and vapors away solvent, makes hydrophilic macromolecule more closely be adsorbed on film surface and fenestra inwall.The polymeric
membrane that will vapor away again solvent immerses containing in the aqueous solution of crosslinking agent and carries out cross-linking reaction.Because
hydrophilic macromolecule is not dissolved in water, avoided having free hydrophilic macromolecule to participate in reaction in fenestra, thereby the flux of having
avoided plug-hole to cause fully descend.

[summary of the invention]

[technical problem that will solve]

The purpose of this invention is to provide a kind of porous film surface permanent hydrophilic method of modifying, and the perforated membrane obtained by the
method.

[technical scheme]

The present invention is achieved through the following technical solutions.

The present invention relates to a kind of porous film surface permanent hydrophilic method of modifying, the step of the method is as follows:

A, 100 parts of gross weights of preparation containing vinyl alcohol segmented polymer solution: will be dissolved in the mixed solvent is comprised of the first solvent
and deionized water containing the vinyl alcohol segmented polymer, what obtain containing by the 0.2-20 weight portion that vinyl alcohol segmented polymer, 60-94.8
weight portion the first solvent and 5-30 parts by weight of deionized water form contains vinyl alcohol segmented polymer solution;

Described perforated membrane is polyolefin, polyamide, fluorinated polymer, polyether sulfone, cellulose, PEI, polyacrylonitrile, polyvinyl chloride or ceramic porous
membrane;

Described containing the vinyl alcohol segmented polymer be one or more be selected from polyvinyl alcohol, ethylene-vinyl alcohol copolymer, AA-E alcohol copolymer,
vinyl alcohol-vinyl acetate co-polymer, polyvinyl formal, polyvinyl acetal, polyvinyl formal acetal, polyvinyl butyral resin containing the vinyl alcohol segmented polymer;

Described the first solvent is selected from one or more in methyl alcohol, ethanol, isopropyl alcohol or normal propyl alcohol;

B, described perforated membrane is immersed in to prepared by steps A containing in vinyl alcohol segmented polymer solution, soak 5-24h under temperature 15-60
℃, generate one deck containing vinyl alcohol segmented polymer layer on described perforated membrane, then separating belt is containing the perforated membrane
of vinyl alcohol segmented polymer layer;

C, the perforated membrane that step B is obtained dry naturally, allow the solvent of its perforated membrane absorption evaporate, and make to be adsorbed on porous
film surface and inner hole wall containing the vinyl alcohol segmented polymer;

D, the perforated membrane dried that step C is obtained are immersed in the aqueous solution that contains 0.1-10% crosslinking agent by weight, allow and carry out
cross-linking reaction 0.5-5h containing vinyl alcohol segmented polymer and described crosslinking agent under temperature 15-60 ℃, form the perforated membrane
with network-like hydrophilic polymer thin layer;

Described crosslinking agent is selected from one or more in borax, formaldehyde, glyoxal or glutaraldehyde;

E, the perforated membrane that step D is obtained separate with the solution that contains crosslinking agent, then put into deionized water and carry out rinsing,
remove unreacted crosslinking agent, obtain a kind of perforated membrane with hydrophilic coating, make described porous film surface complete the permanent
hydrophilic modification.

In the present invention, described perforated membrane is hollow fiber porous film or plate porous membrane.

According to a kind of preferred embodiment, in steps A, contain the vinyl alcohol segmented polymer 50~80 ℃ of temperature and keep the condition of constant
temperature to be dissolved.

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Preferably, in steps A, the described vinyl alcohol segmented polymer solution that contains is comprised of containing vinyl alcohol segmented polymer, 70-85 weight
portion the first solvent and 10-20 parts by weight of deionized water the 2-16 weight portion.

Preferably, in step B, described perforated membrane soaks 10-18h containing in vinyl alcohol segmented polymer solution described under temperature 25-40 ℃.

Preferably, in step C, described perforated membrane dries under temperature 15-25 ℃ in the air of natural flow.

Preferably, in step D, the perforated membrane dried is immersed in the aqueous solution that contains 2-8% crosslinking agent by weight.

Preferably, in step D, containing vinyl alcohol segmented polymer and described crosslinking agent, under temperature 20-40 ℃, carry out cross-linking reaction 1.5-3.0h.

Preferably, in step e, rinsing in deionized water 3-5 time for the perforated membrane obtained at step D, the amount of deionized water of use is 5-10 with the ratio of its
perforated membrane amount by weight.

The perforated membrane of the surperficial permanent hydrophilic obtained according to said method, its pure water flux is 1300-1900L/m 2h0.1MPa, contact angle is
50-55 °.

Below the present invention will be described in more detail.

The invention provides a kind of porous film surface hydrophilic modification method.More specifically, the solution immersion perforated membrane of a kind of use
containing polymer, the first solvent and the deionized water of vinyl alcohol segment is provided, then evaporation is except desolventizing, make hydrophilic polymer be
adsorbed on porous film surface and fenestra surface formation thin layer, carry out cross-linking reaction with the hydrophilic macromolecule of crosslinking agent and
film adsorption again, form network-like hydrophilic polymer thin layer.The detailed step of the method is:

A, preparation are containing vinyl alcohol segmented polymer solution: will be dissolved in the mixed solvent is comprised of the first solvent and deionized water
containing the vinyl alcohol segmented polymer, what obtain containing by the 0.2-20 weight portion that vinyl alcohol segmented polymer, 60-94.8 weight portion the
first solvent and 5-30 parts by weight of deionized water form contains vinyl alcohol segmented polymer solution;

Described perforated membrane is polyolefin, polyamide, fluorinated polymer, polyether sulfone, cellulose, PEI, polyacrylonitrile, polyvinyl chloride or ceramic porous
membrane;

Described containing the vinyl alcohol segmented polymer be one or more be selected from polyvinyl alcohol, ethylene-vinyl alcohol copolymer, AA-E alcohol copolymer,
vinyl alcohol-vinyl acetate co-polymer, polyvinyl formal, polyvinyl acetal, polyvinyl formal acetal, polyvinyl butyral resin containing the vinyl alcohol segmented polymer;

Described the first solvent is selected from one or more in methyl alcohol, ethanol, isopropyl alcohol or normal propyl alcohol.

B, described perforated membrane is immersed in to prepared by steps A containing in vinyl alcohol segmented polymer solution, soak 5-24h under temperature 15-60
℃, generate one deck containing vinyl alcohol segmented polymer layer on described perforated membrane, then separating belt is containing the perforated membrane
of vinyl alcohol segmented polymer layer;

C, the perforated membrane that step B is obtained dry naturally, allow the solvent of perforated membrane absorption evaporate, and make to be adsorbed on porous
film surface and inner hole wall containing the vinyl alcohol segmented polymer;

D, the perforated membrane dried that step C is obtained are immersed in the aqueous solution that contains 0.1-10% crosslinking agent by weight, allow and carry out
cross-linking reaction 0.5-5h containing vinyl alcohol segmented polymer and described crosslinking agent under temperature 15-60 ℃, form the perforated membrane
with network-like hydrophilic polymer thin layer;

Described crosslinking agent is selected from one or more in borax, formaldehyde, glyoxal or glutaraldehyde;

Wherein, the polymer and the aldehyde compound generation cross-linking reaction that contain the vinyl alcohol segment:

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Polymer and borax generation cross-linking reaction containing the vinyl alcohol segment:

These two kinds of reactions all can obtain the perforated membrane with network-like hydrophilic polymer thin layer.

E, the perforated membrane that step D is obtained separate with the solution that contains crosslinking agent, then put into deionized water and carry out rinsing,
remove unreacted crosslinking agent, obtain a kind of perforated membrane of surface hydrophilic modification.

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In the present invention, the polymer in hydrophilic solution contains hydrophily hydroxyl and hydrophobic chain segment, and when polymer solution penetrates into
fenestra, hydrophobic group can partly be adsorbed onto the film surface by hydrophobic effect power.Because this polymer has dissolubility preferably in mixed solvent,
polymer molecule will be in conformation comparatively freely, and molecule can not firmly be adsorbed in porous film surface.The mixed solvent innovatively the first
solvent and deionized water formed in the present invention evaporates fully, and contain vinyl alcohol polymer and will be adsorbed in porous film surface and form thin
coating evaporation process completes after, thus formation adsorption layer comparatively firmly.But, if do not carry out cross-linking reaction, even temporarily can be
adsorbed on perforated membrane containing the polymer of vinyl alcohol segment, but, in actual filtration, film is subject to the thermodynamics motion of current
continuous erosion and macromolecule itself, the polymer of absorption also can come off gradually.Therefore to adopt crosslinkable and polymer containing the vinyl
alcohol segment to carry out crosslinked in the present invention, and the hydrophilic polymer thin layer of crosslinked rear formation becomes three-dimensional netted,
can firmly be fixed on porous film surface and fenestra inwall.Due to the mixed solution of this polymer dissolution containing the vinyl alcohol segment in the first
solvent and deionized water composition, be not dissolved in deionized water, thereby in cross-linking process, hydrophilic polymer degree of swelling in water is very
little, does not almost stop up the potential danger of fenestra, crosslinked back aperture changes less.

In the present invention, described perforated membrane is to use dry-wet method or fusion drawn method or thermally induced phase separation to prepare polyolefin,
polyamide, fluorinated polymer, polyether sulfone, cellulose, PEI, polyacrylonitrile, polyvinyl chloride or the Ceramic Hollow Fiber form of pore-forming or the polyolefin
film of flat sheet membrane form.

The perforated membrane of the surperficial permanent hydrophilic obtained according to said method, its pure water flux is 1300-1900L/m 2h0.1MPa, contact angle is
50-55 °.

In the present invention, the tangent line that contact angle refers to the liquid-vapor interface of doing in gas, liquid, solid three joining places is through the angle theta
between liquid and solid-liquid boundary line, in water treatment field, is one of the common counter of the performance of measurement film.

In the present invention, the assay method of pure water flux is measured according to People's Republic of China's ocean industry standard " doughnut miillpore filter
method of testing HY/T 051---1999 ", and probe temperature is 25 ℃, pressure 0.1MPa.

[beneficial effect]

The invention provides a kind of method of perforated membrane hydrophilic modifying.By selecting the hydrophilic macromolecule that can not be dissolved in
separately water to be mixed with hydrophilic processing liquid, film is processed, the hydrophilic macromolecule of this class, containing a certain proportion of
hydrophobic segment, has guaranteed that macromolecule can be adsorbed on hydrophobic polymeric membrane surface smoothly.After immersion completes,
perforated membrane is taken out to the step that solvent evaporates is fallen, make hydrophilic macromolecule can more closely be adsorbed on film surface and
fenestra inwall.Finally adopt the method for chemical crosslinking to make the hydrophilic high mol generation crosslinked, form crosslinked hydrophilic coating.With the
employing grafting of having announced with apply the patent carry out hydrophilic treatment and compare, the hydrophilic treatment method that this patent provides is
avoided plug-hole and the phenomenon that causes flux to reduce fully, the hydrophilic coating of generation is more firm, hydrophilic treatment is effective.

[specific embodiment]

embodiment 1

With dry-Pvdf Microporous Hollow Fiber Membrane that wet method prepares, recording pure water flux is 750L/m 2h0.1MPa, contact angle is 89 °.Polyvinylidene
fluoride film first is immersed in vinyl alcohol-vinyl acetate co-polymer solution, and the component of this solution is 0.2kg vinyl alcohol-vinylacetate+94.8kg ethanol+5kg
deionized water.Soaking temperature is 25 ℃, soak time 10 hours.Then take out and dry, flash-off time is 8h.The perforated membrane that dries is immersed and carry
out crosslinkedly in the glutaraldehyde water solution of 1.0%wt, the glutaraldehyde water solution temperature constant is 30 ℃.After 3 hours, perforated membrane is
taken out, in deionized water, rinsing is 1 hour.Recording its pure water flux is 1300-1400L/m 2h0.1MPa, contact angle is 55 °.

embodiment 2:

The doughnut polychloroethylene film prepared with thermally induced phase separation, pure water flux is 800L/m 2h0.1MPa, contact angle is 93 °.Described film first is
immersed in vinyl alcohol-vinyl acetate solution, and the component of solution is 20kg vinyl alcohol-vinylacetate+60kg methyl alcohol+20kg deionized water.Solution

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temperature is constant is 15 ℃.Soaking temperature is 15 ℃, soaks after 12 hours film is taken out, and be 8h drying time.The glyoxal solution that is 10%wt by 15 ℃ of
concentration of constant temperature again carries out crosslinked, after half an hour, film is taken out, and puts into the deionized water rinsing 2 hours.Recording its
pure water flux is 1780L/m 2h0.1MPa, contact angle is 54 °.

example 3:

With dry-fine film of flat polypropylene that wet method prepares, pure water flux is 750L/m 2h0.1MPa, contact angle is 90 °.Described film first is immersed in the
polyvinyl formal copolymer solution that temperature is 60 ℃, and the component of solution is 16kg polyvinyl formal copolymer+70kg isopropyl alcohol+14kg deionized
water.Soaking temperature is 30 ℃, and soak time is 18 hours.Solvent evaporated dry after film is taken out, then the formalin that is 2.0%wt with 50 ℃ of concentration
of constant temperature carries out crosslinkedly, after 1 hour, taking-up, put into the deionized water rinsing 1 hour.Recording its pure water flux is 1400L/m 2h0.1MPa,
contact angle is 50 °.

embodiment 4:

Identical with embodiment 3, difference is that described film is polyether sulphone hollow fibre film, and pure water flux is 420L/m 2h0.1MPa, contact angle is 92 °, with
borax, replaces formaldehyde, and the borax mass concentration is 2.0%, and all the other are identical.Recording its pure water flux is 1380L/m 2h0.1MPa, contact angle
is 55 °.

embodiment 5:

Identical with embodiment 3, difference is that described film is the polyamide hollow-fibre membrane, and pure water flux is 390L/m 2h0.1MPa, contact angle is 91 °,
and difference is to replace isopropyl alcohol with normal propyl alcohol, and the component of solution is 6kg polyvinyl formal copolymer+64kg isopropyl alcohol+30kg
deionized water, and all the other are identical, and recording caudacoria pure water flux is 1250L/m 2h0.1MPa, contact angle is 50 °.

embodiment 6:

Identical with embodiment 3, difference is to replace polyvinyl formal with polyvinyl acetal, and all the other are identical.Recording its pure water flux is 1430L/m
2h0.1MPa, contact angle is 51 °.

embodiment 7:

Identical with embodiment 3, difference is to replace polyvinyl formal with ethylene-vinyl alcohol copolymer, and all the other are identical.Recording its pure water flux is
1620L/m 2h0.1MPa, contact angle is 54 °.

embodiment 8:

Identical with embodiment 3, difference is to replace polyvinyl formal with the AA-E alcohol copolymer, and all the other are identical.Recording its pure water flux is
1380L/m 2h0.1MPa, contact angle is 56 °.

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https://patents.google.com/patent/CN102423642B/en?assignee=origin+water 8/15
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CN103418254B * 2012-05-21 2015-07-08 中国科学院化学研究所 Method of hydrophilic modification of polyvinylidene fluoride membrane

CN103768958B * 2012-10-19 2015-09-16 中国石油化工股份有限公 A kind of hydrophilic polypropylene hollow fiber microporous membrane and
司 preparation method thereof

CN104788712B * 2015-03-25 2017-10-31 嘉兴学院 A kind of filling perforation polyurethane water-proof moisture permeable
membrane and preparation method thereof

US9649603B2 * 2015-03-31 2017-05-16 Pall Corporation Hydrophilically modified fluorinated membrane (III)

US9724650B2 2015-03-31 2017-08-08 Pall Corporation Hydrophilically modified fluorinated membrane (II)

US9630151B2 2015-03-31 2017-04-25 Pall Corporation Hydrophilically modified fluorinated membrane (V)

CN106422808A * 2015-08-11 2017-02-22 贵阳时代沃顿科技有限公 Super-hydrophilic polyacrylonitrile hollow fiber ultra-filtration membrane and
司 preparation method thereof

CN106474947B * 2016-12-14 2020-01-03 中国科学技术大学 Preparation method of porous ceramic membrane with hydrophobic surface

CN107441965B * 2017-08-11 2020-12-29 杭州科百特过滤器材有限 Preparation method of porous membrane


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CN108031306A * 2017-12-23 2018-05-15 刘顶康 A kind of polyvinyl chloride filter membrane with hydrophilic stability

https://patents.google.com/patent/CN102423642B/en?assignee=origin+water 9/15
8/13/23, 1:58 PM CN102423642B - Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same - Google Patents

CN108636131A * 2018-05-04 2018-10-12 上海恩捷新材料科技股份 Hydrophilized porous membrane and preparation method thereof
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CN108559124B * 2018-05-22 2021-09-14 上海恩捷新材料科技有限 Surface hydrophilic modified film and preparation method thereof
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CN108993174B * 2018-08-20 2021-07-13 宁波昌祺微滤膜科技有限 Sodium hypochlorite-resistant ePTFE hydrophilic membrane and preparation
公司 method and application thereof

CN109161047B * 2018-09-03 2021-07-09 江苏科技大学 Preparation method of porous permeable membrane of polystyrene or
polystyrene copolymer

CN109503876A * 2018-11-07 2019-03-22 江苏金羿射日新材料科技 A kind of hydrophilically modified method of hydrophobic material
有限公司

CN112044281B * 2019-06-06 2022-05-17 上海恩捷新材料科技有限 Hydrophilic polyethylene microporous membrane and preparation method thereof
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CN111389226B * 2020-04-17 2022-07-05 浙江理工大学 Permanent hydrophilic ultrafiltration membrane and preparation method thereof

CN112138547B * 2020-09-16 2021-11-19 华中科技大学 Semi-interpenetrating network polymer supported membrane, preparation and
application for electric membrane extraction

CN113499691A * 2021-07-21 2021-10-15 苏诺特(苏州)材料科技有 Method for modifying membrane material for organic solvent concentration
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CN114950149A * 2022-06-13 2022-08-30 上海乐纯生物技术有限公 EVOH (ethylene vinyl alcohol) based membrane casting solution and method for
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Concepts

machine-extracted Download Filter table

Name Image Sections Count Query match

membrane title,claims,abstract,description 86 0.000

modification method title,abstract,description 3 0.000

polymer claims,abstract,description 60 0.000

water claims,abstract,description 54 0.000

ethenol claims,abstract,description 51 0.000

deionised water claims,abstract,description 24 0.000

solvent claims,abstract,description 24 0.000

cross linking reagent claims,abstract,description 22 0.000

flux claims,abstract,description 21 0.000

cross linking claims,abstract,description 14 0.000

chemical reaction claims,abstract,description 13 0.000

https://patents.google.com/patent/CN102423642B/en?assignee=origin+water 12/15
8/13/23, 1:58 PM CN102423642B - Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same - Google Patents

hydrophilic polymer claims,abstract,description 10 0.000

coating agent claims,abstract,description 8 0.000

coating method claims,abstract,description 8 0.000

solution claims,description 32 0.000

vinyl polymer claims,description 16 0.000

iso-propanol claims,description 12 0.000

copolymer claims,description 11 0.000

formaldehyde claims,description 9 0.000

aqueous solution claims,description 8 0.000

ethanol claims,description 8 0.000

methanol claims,description 8 0.000

acetyl group claims,description 7 0.000

vinyl group claims,description 7 0.000

Polyvinyl alcohol claims,description 6 0.000

polyolefin claims,description 6 0.000

polyvinyl alcohol claims,description 6 0.000

sodium tetraborate claims,description 6 0.000

sodium tetraborate claims,description 6 0.000

Polyamide claims,description 5 0.000

absorption reaction claims,description 5 0.000

glutaraldehyde claims,description 5 0.000

hollow fiber claims,description 5 0.000

mixed solvent claims,description 5 0.000

polyamide claims,description 5 0.000

polyamide (building material) claims,description 5 0.000

polyvinyl chloride claims,description 5 0.000

https://patents.google.com/patent/CN102423642B/en?assignee=origin+water 13/15
8/13/23, 1:58 PM CN102423642B - Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same - Google Patents

Ethylene vinyl alcohol claims,description 4 0.000

Glyoxal claims,description 4 0.000

Polyether sulfone claims,description 4 0.000

Polyetherimide claims,description 4 0.000

Polyethylenimine claims,description 4 0.000

cellulose claims,description 4 0.000

cellulose claims,description 4 0.000

ceramic claims,description 4 0.000

poly(ether sulfone) claims,description 4 0.000

polyacrylonitrile claims,description 4 0.000

polyetherimide claims,description 4 0.000

polyvinyl chloride claims,description 4 0.000

propanol claims,description 4 0.000

poly(vinyl butyral) polymer claims,description 3 0.000

preparation method claims,description 3 0.000

resin claims,description 3 0.000

resin claims,description 3 0.000

Macromolecule abstract,description 17 0.000

porous material abstract,description 4 0.000

soaking abstract,description 4 0.000

blocking abstract,description 3 0.000

evaporation abstract,description 3 0.000

effects abstract,description 2 0.000

Show all concepts from the description section

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